Storage stable coating composition comprising alkyd resin,esterified inorganic acid and volatile buffer material



United States Patent ILS. Cl. 26021 23 Claims ABSTRACT OF THE DISCLOSURE A coating composition and the method of making the same which includes a combination of an alkyd resin, an urea resin, an inorganic acid and a volatile buffer material. The inorganic acid causes cross-linking of the alkyd and urea resins when the butler material evaporates upon application of the composition as a film.

This is a continuation-in-part application of co-pending application Ser. No. 640,475 filed May 23, 1967, now US. Pat. No. 3,445,410, issued May 20, 1969, which was a continuation-in-part of application Ser. No. 590,207 filed Oct. 28. 1966 (now abandoned).

The combination of an alkyd resin and urea resin will produce a hard surface coating composition inasmuch as these components are capable of cross-linking to provide the desired hard enamel surface. However, these ingredients are normally cured by the application of heat to produce the desired result. Organic acid has been used to trigger the reaction between the alkyd resin and the urea resin, but the shelf life of such a mixture is very limited and the mixture begins to jell after a period of eight hours to three days. Thus, heretofore it has not been possible to apply a paint substance and allow it to air-dry and at the same time obtain the hard finish of the baked-on curing process, unless the organic acid is added to the alkyd resin and urea resin combination at the time of use.

Thus, it is a principal object of this invention to provide an air-drying coating composition which is storage stable.

A further object of this invention is to provide a coating composition and the method of making the same.

A further object of this invention is to provide an airdrying coating composition which is storage stable and which includes a combination of an alkyd resin enamel, an urea resin, an inorganic acid and a volatile bufler material.

A further object of this invention is to provide a coating composition wherein the cross-linking of the alkyd and urea resin is produced by an inorganic acid when a butler material provided therein evaporates upon application of the composition as a film.

A further object of this invention is to provide an airdrying coating composition which results in the hard finish of a baked-on curing process.

A further object of this invention is to provide a coating composition which facilitates easy packaging and handling thereof.

A further object of this invention is to provide a coating composition which is durable in use and attractive in appearance.

3,547,846 Patented Dec. 15, 1970 These and other objects will be apparent to those skilled in the art.

Generally speaking, the coating composition of this invention consists of a combination of an alkyd resin, an urea resin, an inorganic acid and a bufier material and the method of combining the same to produce an airdrying coating composition having the qualities of a baked-on coating composition.

Table I below lists: (1) the preferred ingredients of i the compositions; (2) the permissive percentage range by Weight of the ingredients; and (3) comments. The comments section of Table I lists the preferred ingredients by specific name or otherwise and also lists alternate ingredients which may be substituted for the preferred ingredients. The alternate ingredients have been found to work although somewhat less satisfactorily than the preferred ingredients.

TABLE I Permissive percent range by Preferred material weight Comments Pigment 1 4. 35-45. 0 N on-reactive pigments (such as titanium dioxide. molybdate orange, chrome yellow, phthalocyanme green, or BON maroon). Wettmgagcnts 02-. 097 E.g., soya lecithin, Nuosperse 657. Suspension agent. 25-. 72 E.1g., atlkyl ammonium montmorilom e. Alkyd resin 1 15. 40-16. 20 gbumber of 5 to 9, OH value of Xylene 1 2. 16-4. 15 Boiling range 275-286 F. VM & I naphtha.-." 1 1. 33-5. 66 Boiling range 216288 F. Alkyd resin 1 15. 40-16. 20 Arid number of 5 to 9, OH value of 6-50. Toluene.. 83-3. 28 Boiling range 228-232 F. Alkyd resln 1 23. 42-24. 07 nrmber of 5 to 9, 011 value of 5 6% zirconium drier. 6-. 65 Prefer naphthenates. 6% manganese dric1 2 85-. 37 Do. 6% cobalt drier 6-. 65 Do. Anti-skinning agent .21. 22 E.g., a volatile oxime. Sllp agent 2 2. 0-2. 10 E.g., organo-silicon-oxide polymer Cyclohexanone" 3 1. 44-1. 60 Aromatic 3 1. 67-2. 0 E.g., naphtha (boiling range 316 hydrocarbon. 349 F.). N-butyl alcohol 3 1. 6-1. 7 N-butanol, may be replaced by diisohutyl carbinol. Methyl rsobutyl 3 2. 4-3. 4 E.g., MIBK preferred but other ketone. kctones such as mesityl oxide, methyl ethyl ketone could be utilized. Inorganic acid 2 0. 018-0. 019 30% H2504 solution percentage used is based on alkyd OH value. Buffer agent E.g., morpholine, may be substipiuted by n-substituted morphone. Isobutylated urea- 2. 8-3. 0

formaldehyde resin.

1 Percent by weight of total composition.

2 Percent by weight of alkyd non-volatile Weight.

3 Percent by weight of total vehicle weight.

4 3% of weight of 30% H2804 solution.

The pigment used in this composition will obviously vary according to the desired color of the composition. However, the pigment must be a nonreactive type pigment to obtain the optimum results. The wetting agent will vary with the particular pigment being used but soya lecithin may be used. The suspension agent will also vary with the particular pigment being used.

The alkyd resin must have a hydroxyl (OH) value of 36-50 and-should have an acid number of 5 to 9. The alkyd resin also must be free of epoxidized materials. Xylene, VM&P naphtha and toluene can be used alone or in combination, depending on the end use of the enamel, and can range from 12.015.0% of the total vehicle Weight. The driers are preferably from the naphthenate class but can be from the octoates or tallates and consist of 6% zirconium drier, 6% cobalt drier and 6% manganese drier. The anti-skinning agent is preferably a volatile oxime. The slip agent is preferably an organo-siliconoxide polymer. Cyclohexanone (ketohexamethylene) is extremely important to the composition and no substitution should be made. The aromatic hydrocarbons used in this composition should have boiling ranges of 316-349" F., 275286 F., and 228-232 F., and xylene and toluene are of these boiling ranges, and are readily available on the market; the naphtha should have a boiling range of 2l6288 F. N-butyl alcohol is also an important ingredient of the composition which can be replaced by diisobutyl carbinol and alcohols of similar structure that are effective solvents for urea and melamine resins.

Ketones such as mesityl oxide or methyl ethyl ketone can be used with varying amounts of success, however, MIBK is preferred for the best results. The 30% H 80 solution listed in Table I is extremely important to this composition. The percentage to be used in this composition is based on alkyd OH value and is preferably .031 to .032% of the alkyd non-volatile weight. The composition by weight of the 30% H 50 solution is 35% benzol, 35% butanol and 30% H 80 To esterify the H 80 the benzol and butanol must be first blended and then the H SO slowly added thereto and blended therewith. It is possible that hydrochloric, hydrobromic or nitric acid could be substituted for the sulfuric acid, but sulfuric acid is vastly superior.

The morpholine used as a buffer material can be replaced in the proportion indicated by n-substituted morpholines such as a n-methyl morpholine, n-aminopropyl morpholine, or n-hydroxethyl morpholine. Also, monoethanolamine, diethanolamine or triethanolamine may be used as a substitute for morpholine in the proportions indicated. However, none of the beforementioned buffer materials will work as satisfactorily as morpholine. The morpholine preferably comprises 3% by weight of the 30% H 80 solution.

The urea resin is preferably isobutylated urea resin and its use is preferred over other specific urea-formaldehyde resins which could serve as inferior substitutes.

The preferred alkyd resin is -45 parts of a copolymer of a monomer such as acrylonitrile or methyl methacrylate in a continuum representing a solution of alkyd polymer derived from 4570% of unsaturated vegetable oil fatty acids; the remainder being polymeric ester derived from 15-30% dibasic acid (phthalic, isophthalic, fumeric or maleic) and a tri-functional polyol like glycerol, trimethylol propane or tri-methylol ethane. The resin is controlled by polymerization of the acrylic monomer added in one or more increments to the alkyd base. The interpolymerization of the acrylic polymerization and the polymeric ester, at 60% solids in xylol has the following physical properties:

Non-volatile-60%1 Solvent-Xylol Viscosityl 6'20 stokes Acid value (on N.V.)67.5 Color-4 Wt./gal.-8.34 lbs.

OH range45 average The composition is made in the following manner. The pigment, wetting agents, suspension agents, the first (Table I) alkyd resin material, Xylene and VM&P naphtha are charged to dispersing equipment which can be either a porcelain ball mill, a sand mill or a roller mill. The material is then taken to a dispersion-type enamel grind. This mixture is then added to the second (Table I) alkyd resin material and mixed for 15 to minutes. The Toluene is used to rinse or clean the equipment and is then added to the mixture. The third (Table I) alkyd resin material is added to the batch while it is mixing and the mixing is continued for another 15 minutes. To this point, the procedure has been normal to regular paint production. Zirconium drier, cobalt drier, manganese drier and the anti-skinning agent are thoroughly blended and then added to the batch with strong agitation. The cyclohexanone, aromatic hydrocarbon, N-butyl alcohol, methyl isobutyl ketone, H 80 solution, and approximately one-half of the buffer material are thoroughly blended and slowly added to the batch which is allowed to mix while the blending operation was completed. The 30% H solution should be previously prepared by mixing benzol and butanol together and then slowly adding H 80 This solution must cool to room temperature before use.

The remainder of the bufier material is then added to the batch. The slip agent can then be added or it could have been added to the batch after the drier blend was added thereto. The batch is then thoroughly mixed for 15 minutes. The isobutylated urea resin is then added While the batch is mixing and the mixing is continued for onehalf hour.

It is imperative that the urea resin be added to the mixture at this point as a cheesy type coating will result if otherwise prepared. It should be noted that the various ingredients and percentages thereof can be and will be varied slightly depending on the desired end product. Table I lists those ingredients and percentages which will result in the most satisfactory product. Compositions which are less than satisfactory will be obtained when said ingredients and percentages are varied to any degree beyond that indicated. The percent by weight of the alkyd resin can vary in the dilferent production stages but the total is preferably 55.31 plus or minus 1%.

The product is then placed in suitable containers for storage and/or shipment. Cross-linking of the alkyd and urea resin is prevented by the buffer agent during the storage of the coating compositions thereby preventing the composition from jelling. When the coating composition is applied as a film at room temperatures of 50 F. to 80 F., the buffer material evaporates thereby permitting the inorganic acid to trigger the reaction between the urea and alkyd resins which results in a cross linking thereof. The resulting coating is comparable to those coatings produced by the baked-on" curing process. When applied at normal room temperatures, the coating will be dust free in approximately 30-60 minutes depending upon the humidity. The coating continues to cure for about 72 hours and will be maximum cured by that time.

It can be appreciated that the buffering feature of this composition greatly increases the storage life of the composition as well as conveniently providing a finish which is comparable to the baked-on finishes. Thus, it can be seen that the composition accomplishes at least all of its stated objectives.

I claim:

1. A storage stable coating composition, comprising:

a quantity of an alkyd resin having a hydroxyl value of between 36 and 50, said alkyd resin comprising a copolymer of an acrylic monomer in a continuum representing a solution of alkyd polymer,

a quantity of an urea-formaldehyde resin,

a quantity of an esterified inorganic acid,

and a quantity of an amine buffer material inhibiting the cross-linking of said alkyd resin and said urea resin by said esterified inorganic acid,

said buffer material being volatile at normal room temperatures when exposed to the atmosphere so that exposure of said coating composition to the atmosphere as a layer of film at normal room temperature will permit the evaporation of said buffer material and will permit the subsequent cross-linking of said alkyd resin and said urea resin to form a hard and durable film coating.

2. The composition of claim .1 wherein the esterified inorganic acid is comprised of an esterified H 80 solution.

3. The composition of claim 2 wherein the inorganic acid comprises .031 to .032% by weight of the alkyd nonvolatile weight.

4. The composition of claim 1 wherein said esterified inorganic acid is the ester of H 50 benzol and butanol.

5. The composition of claim 1 wherein the butter material is comprised of morpholine.

6. The composition of claim wherein the morpholine comprises 3% by weight of the esterified inorganic acid.

7. The composition of claim 1 wherein the buffer material is comprised of morpholine and the esterified inorganic acid is comprised of esterified H 80 8. The composition of claim 1 wherein said ureaformaldehyde resin is isobutylated.

9. The composition of claim 1 wherein the urea-formaldehyde resin comprises 4.4 to 4.5% of the total vehicle weight.

10. The composition of claim 1 wherein the alkyd resin comprises 53.8 to 57.3% by weight of the total composition.

11. The composition of claim 1 wherein the alkyd resin has an acid number of between 5 and 9, inclusive.

12. The composition of claim 1 wherein said alkyd resin is further comprised of a copolymer of an acrylic monomer in a continuum representing a solution of alkyd polymer derived from 45 to 70% of unsaturated vegetable oil fatty acids, the remainder of the alkyd resin being a polymeric ester derived from to dibasic acid and a trifunctional polyol.

13. The method of making an air-drying storage stable coating composition, comprising the following steps:

esterifying a quantity of inorganic acid,

mixing a quantity of an alkyd resin material com prising a copolymer of an acrylic monomer in a continuum representing a solution of alkyd polymer having a hydroxal value between 36 and with said esterified inorganic acid,

mixing a quantity of an amine butter material with the mixture of said alkyd resin and esterified inorganic acid,

and mixing a quantity of an urea-formaldehyde resin material with the alkyd resin-esterified inorganic acidbuffer material mixture,

said buffer material preventing the cross-linking of the alkyd resin and urea resin by the esterified inorganic acid until the composition is applied as a film thereby permitting the bufier material to evaporate.

'14. The method of claim 13 wherein said inorganic acid is esterified by benzol and butanol.

15. The method of claim 13 wherein the inorganic acid is comprised of a H SO solution.

16. The method of claim 15 wherein the H 50 solution comprises .031 to .032% by weight of the alkyd nonvolatile weight.

17. The method of claim 16 wherein the buffer material is comprised of morpholine, said morpholine comprising .3 by weight of the H solution.

18. The method of claim 13 wherein said inorganic acid is H 80, and is esterified by benzol and butanol.

19. The method of claim 18 wherein said benzol and said butanol are first blended together and the H SO is then blended to the mixture of said benzol and said butanol.

20. The method of claim 13 wherein the buffer material is comprised of morpholine.

21. The method of claim 13 wherein the alkyd resin material comprises 53.8 to 57.3% by weight of the total mixture.

22. The method of claim 13 wherein the alkyd resin has an acid number of between 5 and 9, inclusive.

23. The method of claim 13 wherein the urea resin is comprised of an isobutylated urea, said urea comprising 4.4 to 4.5 by weight of the total vehicle weight.

References Cited UNITED STATES PATENTS 2,871,209 l/1959 Shelley 260850 2,877,130 3/1959 Caron ct a1 26022 3,196,119 7/1965 Boller et al 26022 3,287,293 11/1966 Dalibor 26022 3,309,327 3/1967 Gayer 26021 3,317,474 5/1967 Jones 260850 3,338,743 8/1967 Laganis 260850 3,366,563 1/1968 Hart et al 26022 3,445,410 5/1969 Coulter 26021 DONALD E. CZAJA, Primary Examiner R. W. GRIFFIN, Assistant Examiner US. Cl. X.R. 

